The present invention relates to amidine compounds and their use as pesticides.
Various pesticides have been used for the control of pests including harmful insects, acarines, and nematodes. There have been drastic changes in the control of pests, such as development of new control systems for labor-saving, necessity for paying attention to influences on the environment, and occurrence of resistance to chemical agents in the target pests. Accordingly, development of chemical agents with novel structure or mechanism of action has been eagerly desired. An objective of the present invention is to provide novel compounds having insecticidal, acaricidal, and nematocidal activity, as well as novel pesticides containing these compounds as active agents.
Under these circumstances, the present inventors have extensively studied. As a result, they have found that amidine compounds of formula I as depicted below have excellent pesticidal effects, i.e., insecticidal, acaricidal, and nematocidal activity, thereby completing the present invention.
Thus the present invention provides amidine compounds of formula I (hereinafter referred to as the present compound(s)): 
wherein X and Y are the same or different and are independently halogen, nitro, cyano, or C1-C6 alkyl; Z is C1-C6 haloalkyl or C1-C6 haloalkoxy; R1 is hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, or a group of formula: S(O)nxe2x80x94R5 (wherein R5 is C1-C6 alkyl or C1-C6 haloalkyl; and n is 0, 1, or 2); R2 and R3 are the same or different and are independently halogen or C1-C6 haloalkyl; and R4 is a group of formula: NR6R7 or Nxe2x95x90CR8R9 (wherein R6 is hydrogen, C1-C6 alkyl, (C1-C6 alkoxy)-carbonyl, (C1-C6 alkoxy) C1-C6 alkyl, or C2-C6 acyl; R7 is hydrogen, C1-C6 alkyl, (C1-C6 alkoxy)carbonyl, or C2-C6 acyl; R8 is C1-C6 alkyl or hydrogen; and R9 is C1-C6 alkoxy, C1-C6 alkyl, or di(C1-C6 alkyl)amino); and pesticides containing these amidine compounds as active ingredients.
Specific examples of the substituents in the present compounds are as follows.
The xe2x80x9chalogenxe2x80x9d may include fluorine, chlorine, and bromine atoms.
The xe2x80x9cC1-C6 alkylxe2x80x9d may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, and hexyl groups.
The xe2x80x9cC1-C6 haloalkylxe2x80x9d may include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, difluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, bromodifluoromethyl, dibromofluoromethyl, chlorofluoromethyl, bromofluoromethyl, dichloromethyl, 2-chlorotetrafluoroethyl, 2-bromotetrafluoroethyl, and 2,2,2-trifluoroethyl groups.
The xe2x80x9cC1-C6 haloalkoxyxe2x80x9d may include trifluoromethoxy, pentafluoroethoxy, and difluoromethoxy groups.
The xe2x80x9c(C1-C6 alkoxy)carbonylxe2x80x9d may include methoxycarbonyl and ethoxycarbonyl groups.
The xe2x80x9c(C1-C6 alkoxy) C1-C6 alkylxe2x80x9d may include methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, isobutoxymethyl, 2-methoxyethyl, 1-methoxy-2,2-dimethylpropyl, 1-ethoxy-2,2-dimethylpropyl, 1-methoxy-1,2,2-trimethylpropyl and 1-ethoxy-1,2,2-trimethylpropyl groups.
The xe2x80x9cC2-C6 acylxe2x80x9d, referring also to (C1-C5 alkyl)carbonyl, may include acetyl, propanoyl, butanoyl, 3-methylbutanoyl, 2-methylpropanoyl, and pentanoyl groups.
The xe2x80x9cC1-C6 alkoxyxe2x80x9d may include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups.
The xe2x80x9cdi(C1-C6 alkyl)aminoxe2x80x9d may include dimethylamino, ethyl(methyl)amino, diethylamino, and dipropylamino groups.
Preferred substituents in the present compounds from the viewpoints of high insecticidal and acaricidal activity are as follows:
Each of X and Y may preferably be a halogen atom or a nitro group;
Z may preferably be a C1-C6 haloalkyl group, specifically a trifluoromethyl group;
R1 may preferably be a C1-C6 haloalkyl group;
Each of R2 and R3 may preferably be a halogen atom;
R4 may preferably be an amino group.
The following will describe some production processes for the present compounds. The present compounds can be produced, for example, by one of production processes 1 to 5 as described below.
Production Process 1
The present compounds wherein R4 is a group of formula: NR6R7 can be produced by reacting a compound of formula II: 
wherein X, Y, Z, R1, R2, and R3 are as defined above; and R10 is halogen (e.g., chlorine, bromine, iodine), with a compound of formula III: 
wherein R6 and R7 are as defined above, or a salt thereof in the presence of a base without any solvent or in a solvent.
The reaction is usually carried out at a temperature of about xe2x88x925xc2x0 C. to 150xc2x0 C. for 1 minute to 24 hours. The amounts of reagents to be used in the reaction are usually 1 to 10 moles of compound III or a salt thereof and 1 to 10 moles of a base, relative to 1 mole of compound II. When compound III is allowed to act by itself as a base, this compound may be used in an amount of 2 mole to an excessive amount.
The base may include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; and tertiary amines such as triethylamine.
The solvent which can be used in the reaction may include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; nitro compounds such as nitroethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulforane; water; and mixtures thereof.
After completion of the reaction, the reaction mixture is poured into water, followed by post-treatment including, for example, extraction with an organic solvent and evaporation of the organic layer, to give a product of the desired present compound. The product may be purified by chromatography, recrystallization, or any other technique.
Compound II can be produced by reacting a compound of formula IV: 
wherein X, Y, Z, R1, R2, and R3 are as defined above, with a halogenating agent according to the known methods (see, e.g., JP-A 8-295663).
The halogenating agent may include phosphorus pentachloride, phosphorus oxychloride, and triphenylphosphine-carbon tetrachloride.
The reaction is usually carried out at a temperature of about xe2x88x925xc2x0 C. to 150xc2x0 C. for 1 to 24 hours. The amounts of reagents to be used in the reaction are 1 mole to an excessive amount of a halogenating agent, relative to 1 mole of compound IV.
The solvent which can be used in the reaction may include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether; acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulforane; and mixtures thereof.
After completion of the reaction, the reaction mixture is poured into water, followed by post-treatment including, for example, extraction with an organic solvent and evaporation of the organic layer, to give a product of the desired compound II. The product may be purified by chromatography, recrystallization, or any other technique.
Compound IV can be produced as shown in the following scheme: 
wherein X, Y, Z, R1, R2, R3, and R10 are as defined above; and R11 is C1-C6 alkyl.
Ester compound VI can be produced from carboxylic acid compound V according to the known methods (see, e.g., J. Org. Chem. 55, 812 (1990); Tetrahedron 52, 157 (1996)).
Amide compound VII can be produced from ester compound VI according to the known methods (see, e.g., J. Org. Chem. 51, 332 (1986); Tetrahedron Lett. 34, 7195 (1993)).
Acid halide VIII can be produced from carboxylic acid compound I according to the known methods (see, e.g., J. Org. Chem. 54, 6096 (1989); J. Fluorine Chem. 75, 35 (1995)).
Amide compound III can be produced from acid halide IV according to the known methods (see, e.g., J. Org. Chem. 60, 1319 (1995); J. Fluorine Chem. 84, 135 (1997)).
Compound IV can be produced by reacting acid halide VIII with a compound of formula X: 
wherein X, Y, and Z are as defined above, according to the known methods (see, e.g., Shin-Jikken Kagaku Koza (Maruzen), vol. 14 [II], pp. 1142-1145).
Compound IV can be produced by reacting acid anhydride IX with compound X according to the known methods (see, e.g., JP-A 8-295663).
Compound IV can also be produced by reacting amide compound VII with a compound of formula XI: 
wherein X, Y, and Z are as defined above; and R12 is a leaving group or atom (e.g., fluorine, chlorine, bromine, iodine, methoxy, trifluoromethylsulfonyloxy, methanesulfonyloxy), usually in the presence of a base in a solvent, and if necessary, in the presence of a catalyst.
The reaction is usually carried out at a temperature of about xe2x88x925xc2x0 C. to 150xc2x0 C. for 10 minutes to 24 hours. The amounts of reagents to be used in the reaction are usually 1 to 10 moles of amide compound VII and 1 mole to a large excess of a base, relative to 1 mole of compound XI.
The base may include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; and tertiary amines such as triethylamine, pyridine, 4-dimethylaminopyridine, and N,N-dimethylaniline.
The solvent may include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; nitro compounds such as nitroethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulforane; water; and mixtures thereof.
The catalyst which is used, if necessary, may include crown ethers and potassium fluoride.
After completion of the reaction, the reaction mixture is poured into water, followed by post-treatment including, for example, extraction with an organic solvent and evaporation of the organic layer, to give a product of the desired compound IV. The product may be purified by chromatography, recrystallization, or any other technique.
Production Process 2
The present compounds wherein R4 is amino can be produced by reacting a compound of formula XI with a compound of formula XII: 
wherein R1, R2, and R3 are as defined above, usually in the presence of a base in a solvent, and if necessary, in the presence of a catalyst.
The reaction is usually carried out at a temperature of xe2x88x925xc2x0 C. to 150xc2x0 C. for 10 minutes to 24 hours. The amounts of reagents to be used in the reaction are usually 1 to 10 moles of compound XII and 1 mole to a large excess of a base, relative to 1 mole of compound XI.
The base may include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; and tertiary amines such as triethylamine, pyridine, 4-dimethylaminopyridine, and N,N-dimethylaniline.
The solvent may include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; nitro compounds such as nitroethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulforane; water; and mixtures thereof.
The catalyst which is used, if necessary, may include crown ethers and potassium fluoride.
After completion of the reaction, the reaction mixture is poured into water, followed by post-treatment including, for example, extraction with an organic solvent and evaporation of the organic layer, to give a product of the desired present compound. The product may be purified by chromatography, recrystallization, or any other technique.
Compound XII can be produced according to the known methods (see, e.g., J. Org. Chem. 30, 3729 (1965)).
Production Process 3
The present compounds wherein R4 is a group of formula: NHR13 or N(R13)2 and R13 is C1-C6 alkyl, (C1-C6 alkoxy)carbonyl, (C1-C6 alkoxy) C1-C6 alkyl, or C2-C6 acyl can be produced by the present compounds wherein R4 is amino (hereinafter referred to as compound A) with a compound of formula XIII:
R13xe2x80x94R14xe2x80x83xe2x80x83XIII 
wherein R13 is as defined above and R14 is a leaving group or atom (e.g., chlorine, bromine, iodine, trifluoromethylsulfonyloxy, methanesulfonyloxy), usually in the presence of a base in a solvent.
The reaction is usually carried out at a temperature of xe2x88x925xc2x0 C. to 150xc2x0 C. for 1 to 24 hours.
When the present compounds wherein R4 is a group of formula: NHR13 are produced, the amounts of reagents to be used in the reaction are usually 0.8 to 1 mole of compound XIII and 0.8 to 10 moles of a base, relative to 1 mole of compound A.
When the present compounds wherein R4 is a group of formula: N(R13)2 are produced, the amounts of reagents to be used in the reaction are usually 2 to 10 mole of compound XIII and 2 to 10 moles of a base, relative to 1 mole of compound A.
The base may include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; and tertiary amines such as triethylamine, pyridine, 4-dimethylaminopyridine, and N,N-dimethylaniline.
The solvent which can be used in the reaction may include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; nitro compounds such as nitroethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulforane; water; and mixtures thereof.
After completion of the reaction, the reaction mixture is poured into water, followed by post-treatment including, for example, extraction with an organic solvent and evaporation of the organic layer, to give a product of the desired present compound. The product may be purified by chromatography, recrystallization, or any other technique.
Production Process 4
The present compounds wherein R4 is a group of formula: NR13R15, R18 is as defined above, and R15 is C1-C6 alkyl, (C1-C6 alkoxy)carbonyl, (C1-C6 alkoxy) C1-C6 alkyl, or C2-C6 acyl can be produced by the present compounds wherein R4 is a group of formula: NHR13 (hereinafter referred to as compound B) with a compound of formula XIV:
R15xe2x80x94R14xe2x80x83xe2x80x83XIV 
wherein R14 and R15 are as defined above, usually in the presence of a base in a solvent.
The reaction is usually carried out at a temperature of xe2x88x925xc2x0 C. to 150xc2x0 C. for 1 to 24 hours. The amounts of reagents to be used in the reaction are usually 1 to 10 moles of compound XIV and 1 to 10 moles of a base, relative to 1 mole of compound B.
The base may include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; and tertiary amines such as triethylamine, pyridine, 4-dimethylaminopyridine, and N,N-dimethylaniline.
The solvent which can be used in the reaction may include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; nitro compounds such as nitroethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulforane; water; and mixtures thereof.
After completion of the reaction, the reaction mixture is poured into water, followed by post-treatment including, for example, extraction with an organic solvent and evaporation of the organic layer, to give a product of the desired present compound. The product may be purified by chromatography, recrystallization, or any other technique.
Production Process 5
The present compounds wherein R4 is a group of formula: Nxe2x95x90CR8R9 can be produced by reacting compound A with a compound of formula XV:
(R16O)2CR8R9xe2x80x83xe2x80x83XV 
wherein R8 and R9 are as defined above and R16 is C1-C6 alkyl, or a compound of formula XVI:
Oxe2x95x90CR8R9xe2x80x83xe2x80x83XVI 
wherein R8 and R9 are as defined above, in the presence of an acid catalyst, without any solvent or in a solvent.
The reaction is usually carried out at a temperature of xe2x88x925xc2x0 C. to 150xc2x0 C. for 1 to 24 hours. The amounts of reagents to be used in the reaction are usually 1 to 10 moles of compound XV or XVI and 0.01 to 1 mole of an acid catalyst, relative to 1 mole of compound A.
The acid catalyst may include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid and p-toluenesulfonic acid; and aprotic acids such as boron trifluoride.
The solvent which can be used in the reaction may include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether; aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; nitro compounds such as nitroethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and N,N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulforane; water; and mixtures thereof.
After completion of the reaction, the reaction mixture is poured into water, followed by post-treatment including, for example, extraction with an organic solvent and evaporation of the organic layer, to give a product of the desired present compound. The product may be purified by chromatography, recrystallization, or any other technique.
The present compounds may have structural isomers with respect to the double bond as depicted below, and both isomers are embraced by the present invention. 
The present compounds wherein R4 is a group of formula: NR6R7 and R6 is hydrogen may have tautomers as depicted below, and these tautomers are embraced by the present invention. 
Specific examples of the present compounds are those listed in Tables 1 to 13 below. 
The present compounds can exhibit controlling activity against pests including harmful arthropods (e.g., harmful insects and acarines) and harmful nematodes. Specific examples of the pests are as follows:
Isopoda:
Oniscus asellus, Armadillidium vulgare, Porcellio scaber, etc.;
Diplopoda:
Blanilus guttulatus etc.;
Chilopoda:
Geophilus carpophagus, Scutigera spp., Scolopendra suhspinipes, Thereunema spp., etc.;
Symphyla:
Scutigerella immaculata etc.;
Thysanura:
Ctenolepisma villosa, Lepisma saccharina, etc.;
Psocoptera:
Trogium pulsatorium etc.;
Collembola:
Onychiurus armatus etc.;
Isoptera:
Mastotermitidae; Termopsidae such as Zootermopsis, Archotermopsis, Hodotermopsis (e.g., Hodotermopsis japonica), and Porotetmes; Kalotermitidae such as Kalotermes, Neotermes (e.g., Neotermes koshuensis), Cryptotermes (e.g., Cryptotermes domesticus), Incisitermes (e.g., Incisitermes minor), and Glyptotermes (e.g., Glyptotermes satsumaensis, G. nakajimai, G. fuscus); Hodotermitidae such as Hodotermes, Microhodotermes, and Anacanthotermes; Rhinotermitidae such as Reticulitermes (e.g, Retitulitermes speratus, R. sp, R. flaviceps, R. miyatakei), Heterotermes, Coptotermes (e.g., Coptotermes formosanus), and Schedolinotermes; Serritermitidae; Termitidae such as Amitermes, Drepanotermes, Hopitalitermes, Trinervitermes, Macrotermes, Odontotermes (e.g., Odontotermes formosanus), Microtermes, Nasutitermes (Nasutitermes takasagoensis), Pericapritermes (e.g., Pericapritermes nitobei), and Anoplotermes, etc.;
Dictyoptera:
Blatta orientalis, Periplaneta americana, P. fuliginosa, Leucophaea maderae, Blattella germanica, etc.;
Orthoptera:
Gryllotalpa spp., Acheta domesticus, Teleogryllus emma, Locusta migratoria, Melanoplus differentialis, Schistocerca gregaria, etc.;
Dermaptera:
Labidura riparia, Forficula auricularia, etc.;
Anoplura:
Phthirus pubis, Pediculus humanus, Haematopinus suls, Haematopinus eurysternus, Damalinia ovis, Linognathus spp., Solenopotes spp., etc.;
Mallophaga:
Trichodectes spp., Tromenopon spp., Bovicola spp., Felicola spp., etc.;
Thysanoptera:
Frankliniella intonsa, Thrips tahaci, T. palmi, etc.;
Heteroptera:
Nezara spp., Eurygaster spp., Dysdercus intermedius, Cimex lectularius, Triatoma spp., Rhodnius prolixus, Nezara antennata, Cletus punetiger, etc.;
Homoptera:
Aleurocanthus spiniferus, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevocoryne brassicae, Cryptomyzus ribis, Aphis fabae, Macrosiphum euphorbiae, Myzus persicae, Phorodon humuli, Empoasca spp., Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp., Phylloxera vastatrix, etc.;
Lepidoptera:
Pectinophora gossypiella, Lithocolletis blancardella, Plutella xylostella, Malacosoma neustria, Euproctis subflava, Lymantria dispar, Bucculatrix pyrivorella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Earias insulana, Heliothis spp., Spodoptera exigua, S. litura, Spodoptera spp., Mamestra brassicae, Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tenea translucens, Homona magnanima, Tortrix viridana, etc.;
Coleoptera:
Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes angusticollis, Phyllotreta striolata, Epilachna spp., Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorhynchus sulcatus, Cosmopolites sordidus, Ceuthorhyncidius albosuturalis, Hypera postica, Dermestes spp., Trogoderma spp., Attagenus unicolor; Lyctridae such as Lyctus dentatum, L. planicollis, L. sinensis, L. linearis, L. brunneus, and L. africanus; Meligethes aeneus, Ptinus spp., Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Melolontha mololontha; Scolytidae such as Xyleborus and Scolytoplatypus; Cerambycidae such as Monochamus, Hylotrupes, Hesperophanus, Chlorophorus, Palaeocallidium, Semanotus, Purpuricenus, and Stromatium; Platypodidae such as Crossotarsus and Platypus; Bostrychidae such as Dinoderus, Bostrychus, and Sinoderus; Anobiidae such as Ernobius, Anobium, Xyletinus, Xestobium, Ptilinus, Nicobium, and Ptilineurus; Buprestidae, etc.;
Hymenoptera:
Diprion spp., Hoplocampa spp., Lasius spp., Formica japonica, Vespa spp.; Siricidae such as Urocerus and Sirex, etc.;
Diptera:
Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca domestica, Fannia spp., Calliphora spp., Lucilia spp., Chrysomya spp., Cuterebra spp., Gastrophilus spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Bibio hortulanus, Pegomyia hyoscyami, Ceratitis capitata, Dacus dorsalis, Tipula paludosa, Simulium spp., Eusimulium spp., Phlebotomus spp., Culicoides spp., Chrysops spp., Haematopota spp., Braula spp., Morellia spp., Glossina spp., Wohlfahrtia spp., Sarcophaga spp., Lipoptena spp., Melophagus spp., Muscina spp., etc.;
Siphonaptera:
Xenopsylla cheopis, Ctenocephalides felis, Ctenocephalides canis, Ceratophyllus spp., Pulex spp., etc.;
Arachnida:
Scorpio maurus, Latrodectus mactans, Chiracanthium spp., etc.;
Acarina:
Otodectes spp., Acarus siro, Argas spp., Ornithodoros spp., Ornithonyssus spp., Dermanyssus spp., Eriophyes spp., Haemaphyxalis longicornis, Boophilus microplus, Rhipicephalus spp., Chelacaropsis moorei, Dermatophagoides spp., Hyalomma spp., Ixodes ovatus, Ixodes persulcatus, Psoroptes equi, Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Dermacentor spp., Haemaphysalis spp., Raillietia spp., Pneumonyssus spp., Sternostorma spp., Acarapis spp., Cheyletiella spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Tyrophagus spp., Sarcoptes spp., Notoedres spp., Cytodides spp., Laminosioptes spp., etc.;
Plant parasitic nematodes:
Pratylenchus spp., Grobodera spp., Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Notylenchus spp., Bursaphelenchus lignicolus, etc.
The present compounds can also be used for the effective control of pests having improved resistance to the conventional pesticides.
When the present compounds are used as the active ingredients of pesticides, they may be used as such or in the form of salts (agrochemically acceptable salts with inorganic acids such as hydrochloric acid and sulfuric acid or organic acids such as p-toluenesulfonic acid) without addition of any other ingredients. However, the present compounds are usually mixed with solid carriers, liquid carriers, gaseous carriers or baits, or absorbed in base materials such as porous ceramic plates or nonwoven fabrics, followed by addition of surfactants and other auxiliaries, if necessary, and they are then formulated into various forms, such as oil sprays, emulsifiable concentrates, wettable powders, flowables, granules, dusts, aerosols, fumigants (e.g., foggings), vaporizable formulations, smoking formulations, poison baits, anti-acarine sheets, or resin formulations.
Each of these formulations may usually contain at least one of the present compounds as an active ingredient in an amount of 0.01% to 95% by weight.
The solid carrier which can be used in the formulation may include fine powder or granules of clay materials such as kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, Fubasami clay, and acid clay; various kinds of talc, ceramics, and other inorganic minerals such as sericite, quartz, sulfur, activated carbon, calcium carbonate, and hydrated silica; and chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride.
The liquid carrier may include water; alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and methylnaphthalene; aliphatic hydrocarbons such as hexane, cyclohexane, kerosene, and light oil; esters such as ethyl acetate and butyl acetate; nitrites such as acetonitrile and isobutyronitrile; ethers such as diisopropyl ether and dioxane; acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, trichloroethane, and carbon tetrachloride; dimethyl sulfoxide; and vegetable oils such as soybean oil and cottonseed oil.
The gaseous carrier or propellant may include Freon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide.
The base material for used in poison baits may include bait materials such as grain powder, vegetable oils, sugars, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid; preservatives such as dehydroacetic acid; substances for preventing erroneous eating, such as red pepper powder; and attractant flavors such as cheese flavor and onion flavor.
The surfactant may include alkyl sulfates, alkyl sulfonates, alkyl arylsulfonates, alkyl aryl ethers and their polyoxyethylene derivatives, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol derivatives.
The auxiliaries such as adhesive agents or dispersants may include casein, gelatin; polysaccharides such as starch, gum arabic, cellulose derivatives, and alginic acid; lignin derivatives, bentonite, sugars, and synthetic water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acid.
The stabilizing agent may include PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixtures of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids and their esters.
When the present compounds are used as insecticides, acaricides, or nematocides for agriculture, the amounts for their application are usually in the range of 0.1 to 100 g per 10 ares. For emulsifiable concentrates, wettable powders, flowables, and other similar formulations to be used after dilution with water, the concentrations for their application usually in the range of 1 to 10,000 ppm. The application of granules, dusts, or other similar formulations is carried out as such formulations without dilution. When the present compounds are used as insecticides, acaricides, or nematocides for epidemic prevention, they are applied after dilution with water to concentrations of 0.1 to 500 ppm in the case of emulsifiable concentrates, wettable powders, flowable, or other similar formulations, or they are applied as such in the case of oil sprays, aerosols, fumigants, poisonous baits, anti-acarine sheets, or other similar formulations. These application amounts or concentrations may vary depending upon types of formulations, times, places, and methods of application, kinds of pests, degree of damage, and other factors; they can therefore be increased or decreased without limitation to the above ranges.
When the present compositions are used as insecticides or acaricides for the control of ectoparasites on domestic animals such as cattle and pigs or pets such as cats and dogs, they or their salts may be applied by the known veterinary methods, for example, tablets, capsules, immersion solutions, boli, feed incorporation, suppositories, or injection (e.g., intramuscular, subcutaneous, intravenous, intraperitoneal) for systemic control; or spray, pour-on or spot-on treatment with oily or aqueous solutions, or using articles formed from resin formulations into appropriate shapes such as collars and ear tags for non-systemic control. In these cases, the present compounds are usually applied in their own amounts of 0.01 mg to 100 mg per kg of a host animal.
The present compounds can be used in admixture with, or separately but simultaneously with, other insecticides, nematocides, acaricides, bactericides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners and/or animal feeds.
The insecticide, nematocide and/or acaricide which can be used may include organophosphorus compounds such as Fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl) phosphorothioate], Fenthion [O,O-dimethyl O-(3-methyl-4-(methylthio)phenyl) phophorothioate], Diazinon [O,O-diethyl O-(2-isopropyl-6-methylpyrimidin-4-yl) phosphorothioate], Chlorpyriphos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate], Acephate [O,S-dimethyl acetylphosphoramidothioate], Methidathion [S-((2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-yl)methyl) O,O-dimethyl phosphorodithioate], Disulfoton [O,O-diethyl S-(2-(ethylthio)ethyl) phosphorothioate], DDVP [2,2-dichlorovinyl dimethyl phosphate], Sulprofos [O-ethyl O-(4-(methylthio)phenyl) S-propyl phosphorodithioate], Cyanophos [O-(4-cyanophenyl) O,O-dimethyl phosphorothioate], Dioxabenzofos [2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide], Dimethoate [O,O-dimethyl S-(N-methylcarbamoylmethyl) dithiophosphate], Phenthoate [ethyl 2-((dimethoxyphosphinothioyl)thio)phenylacetate], Malathion [diethyl ((dimethoxyphosphinothioyl)thio)-succinate], Trichlorfon [dimethyl (2,2,2-trichloro-1-hydroxyethyl)phosphonate], Azinphos-methyl [S-((3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-yl)methyl) O,O-dimethyl phosphorodithioate], Monocrotophos [dimethyl (E)-1-methyl-2-(methylcarbamoyl)vinyl phosphate], and Ethion [O,O,Oxe2x80x2,Oxe2x80x2-tetraethyl S,Sxe2x80x2-methylene bis(phosphorodithioate)]; carbamate compounds such as BPMC [2-sec-butylphenyl methylcarbamate], Benfuracarb [ethyl N-(((((2,3-dihydro-2,2-dimethylbenzofuran-7-yl)oxy)carbonyl)methylamino)thio)-N-isopropyl-xcex2-alaninate], Propoxur [2-isopropoxyphenyl N-methylcarbamate], Carbosulfan [2, 3-dihydro-2,2-dimethyl-7-benzo [b]furanyl N-dibutylaminothio-N-methylcarbamate], Carbaryl [1-naphthyl N-methylcarbamate], Methomyl [S-methyl N-((methylcarbamoyl)oxy)thioacetimidate], Ethiofencarb [2-((ethylthio)methyl)phenyl methylcarbamate], Aldicarb [2-methyl-2-(methylthio)propionaldehyde O-(methylcarbamoyl)oxime], Oxamyl [N,N-dimethyl-2-((methylcarbamoyl)oxy)imino-2-(methylthio)acetamide], and Fenothiocarb [S-(4-phenoxybutyl) N,N-dimethylthiocarbamate]; pyrethroid compounds such as Etofenprox [2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether], Fenvalerate [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate], Esfenvalerate [(S)-xcex1-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate], Fenprop athrin [(RS)-xcex1-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], Cypermethrin [(RS)-xcex1-cyano-3-phenoxybenzyl (1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], Permethrin [3-phenoxybenzyl (1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], Cyhalothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate], Deltamethrin [(S)-xcex1-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropanecarboxylate], Cycloprothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate], Fluvalinate [xcex1-cyano-3-phenoxybenzyl N-(2-chloro-xcex1,xcex1,xcex1-trifluoro-p-tolyl)-D-valinate], Bifenthrin [(2-methylbiphenyl-3-yl)methyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate], 2-methyl-2-(4-(bromodifluoromethoxy)phenyl)propyl (3-phenoxybenzyl) ether, Tralomethrin [(S)-xcex1-cyano-3-phenoxylbenzyl (1R)-cis-3-(1, 2,2,2-tetrabromoethyl)-2, 2-dimethylcyclopropanecarboxylate], Silafluofen [(4-ethoxylphenyl) (3-(4-fluoro-3-phenoxyphenyl)propyl)dimethylsilane], d-Phenothrin [3-phenoxybenzyl (1R-cis,trans)-chrysantemate], Cyphenothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (1R-cis,trans)-chrysantemate], d-Resmethrin [(5-benzyl-3-furyl)methyl (1R-cis,trans)-chrysantemate], Acrinathrin [(S)-xcex1-cyano-3-phenoxybenzyl (1R-cis(Z))-(2,2-dimethyl-3-(3-oxo-3-(1, 1,1,3,3,3-hexafluoropropyloxy)propenyl)cyclopropanecarboxylate], Cyfluthrin [(RS)-xcex1-cyano-4-fluoro-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], Tefluthrin [2,3,5,6-tetrafluoro-4-methylbenzyl (1RS-cis(Z))-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate], Transfluthrin [2,3,5,6-tetrafluorobenzyl (1R-trans)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], Tetramethrin [3,4,5,6-tetrahydrophthalimidemethyl (1RS)-cis,trans-chrysantemate], Allethrin [(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (1RS)-cis,trans-chrysantemate], Prallethrin [(S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl (1R)-cis,trans-chrysantemate], Empenthrin [(RS)-1-ethynyl-2-methyl-2-pentenyl (1R)-cis,trans-chrysantemate], Imiprothrin [2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl (1R)-cis,trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate], d-Furamethrin [5-(2-propynyl)furfuryl (1R)-cis,trans-chrysantemate], and 5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate; thiadiazine derivatives such as Buprofezin [2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one); nitroimidazolidine derivatives; Nereistoxin derivatives such as Cartap [S,Sxe2x80x2-(2-(dimethylamino)trimethylene) bis(thiocarbamate)], Thiocyclam [N,N-dimethyl-1,2,3-trithian-5-ylamine], and Bensultap [S,Sxe2x80x2-(2-(dimethylamino)-trimethylene) di(benzenethiosulfonate)]; N-cyanoamidine derivatives such as N-cyano-Nxe2x80x2-methyl-Nxe2x80x2-(6-chloro-3-pyridylmethyl)acetamidine; chlorinated hydrocarbon compounds such as Endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin oxide], xcex3-BHC [1,2,3,4,5,6-hexachlorocyclohexane], and 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylurea compounds such as Chlorfluazuron [1-(3,5-dichloro-4-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)phenyl)-3-(2,6-difluorobenzoyl)urea], Teflubenzuron [1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea], and Fulphenoxron [1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea]; formamidine derivatives such as Amitraz [N,Nxe2x80x2-((methylimino)dimethylidine)-di-2,4-xylidine], and Chlordimeform [Nxe2x80x2-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide]; thiourea derivatives such as Diafenthiuron [N-(2,6-diisopropyl-4-phenoxyphenyl)-Nxe2x80x2-tert-butylcarbodiimide]; phenylpyrazole compounds, Metoxadiazone [5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2(3H)-one], Bromopropylate [isopropyl 4,4xe2x80x2-dibromobenzylate], Tetradifon [4-chlorophenyl 2,4,5-trichlorophenylsulfone], Quinomethionate [S,S-(6-methylquinoxalin-2,3-diyl)dithiocarbonate], Propargite [2-(4-tert-butylphenoxy)cyclohexyl prop-2-yl sulfite], Fenbutatin oxide [bis(tris(2-methyl-2-phenylpropyl)tin)oxide], Hexythiazox [(4RS,5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide], Chlofentezine [3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine], Pyridaben [2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one], Fenpyroximate [tert-butyl (E)-4-(((((1,3-dimethyl-5-phenoxypyrazol-4-yl)methylene)amino)oxy)methyl)benzoate], Tebfenpyrad [N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide], polynactin complexes [e.g., tetranactin, dinactin, trinactin], Pyrimidifen [5-chloro-N-(2-(4-(2-ethoxyethyl)-2,3-dimethylphenoxy)ethyl)-6-ethylpyrimidin-4-amine], Milbemectin, Avermectin, Ivermectin, and Azadilactin [AZAD].